Thioketones



Patented Feb. 20, 1945 i Es PATENT O'FFICE THIIIOKETONES Leslie G. S. Brooker and Grafton Ii. Keyes,

Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N

1 a New Jersey Y'., a' corporation of No Drawing. Application September 13, 1940,

' Serial No. 356,657 In Great Britain December 15, 1939 22 Claims. (01. 260-304) This invention'relates to thioketon'es and to a process for preparing them.

In the copending application, Serial No. 330,580, filed April 14 1940 (now United States Patent" 2,231,659, dated February 11, 1941), of Leslie G. S. Brooker and Frank L. White, halogenovinyl derivatives of the following general formula are described:

' Nags or. NaaSzOa l CH3 The thioketones thus'obtained. sensitize photographic silver halide emulsions,v we have found.

Moreover, we have found. that the thioketones can be converted into useful dye intermediates by treatment with alkyl'salts. I

It is, accordingly, an object of our inventio to provide new thioketones. A further object. is to provide aprocess for-preparing such thicketones.. A further object isto provide new dye intermediates and aprocess' for preparing them. Other objects will become apparent hereinafter. In accordance with our invention, we treat, with a metal or ammonium sulfide or with a metal or ammonium thiosulfate, a compound of the following general formula:

Q l D' CCH- -GX ring; A solid separated out.

wherein D represents aphenylene or a naph thylene group, Qrepresents a sulfur or selenium atom, R and 'R' represent alkyl or aryl groups, X represents an acid radical and X represents halogen. The compounds wherein X represents a halide ion are advantageously employed.

, As metal sulfides, alkali metal and alkaline earth metal sulfides are advantageously 'employed. As metal thiosulfates, alkali metal and alkaline earth metal thiosulfates are advantageously employed. The treatment with thesulfide orthiosulfate is advantageously carried out in the'p'resence of a diluent, such as a lower aliphati'c alcohol, like methyl, ethyl or isopropyl" alcohol. Heat accelerates the reaction of the sulfide or thiosulfa'te with the halogenovinyl compounds. I I

The following examples will serve to illustrate the mailer of.practicing our invention. These examples are not intended to limit our invention. Example 1.-3-ethyZ-2' thiojuroylmethyleneben- 27.1 (1 mol.) or 3-ethy1-2-furoylmethylenebenzothiazoline were suspended'in cc.'of dry benzene. To this suspension'were added 229g,

further minutes at 20 to 25 C. The mixture was then diluted with 100 cc. of diethyl ether and the whole was chilled to 0 C., while stir- The liquids were decanted, and the solid chlorovinyl compound was dissolved in 50 cc. of ethyl alcohol. To this solution was added a solution of 24.8 g. (1 mol.) of sodium thiosulfate (Na2S2O3-5H2O) dissolved in 25 cc. of water. The resulting mixture was heated for ten minutes on' a steam bath. Upon chilling the reaction mixture, the thioketone separated out. It'was filtered off, washed with water (100 00.), methyl alcohol (50 cc.) and finally dried in the air. 16.2 g. (56% yield) were obtained. After two recrystallizations from methobtained as brownish crystals, melting at 163? to 165 C. with decomposition.

Example 2.3-ethyl-2-thiobenzoylmethylenebenzothiazoline 56.2 g. (1 mol.) of 2-benzoylmethylene-3-ethylbenzothiazoline were suspended in 200 cc. of dried benzene. To the resulting suspension, 45.9 g. (1.5 mol.) of phosphorous oxychloride were added, with stirring. The resulting mixture was chilled to C., whereupon the chlorovinyl compound separated out. The chlorovinyl compound was filtered oil and washed well with acetone (300 cc.) It was then dissolved in 100 cc. of 95% ethyl alcohol. The solution was heated to boiling, under reflux, and a solution of 49.6 g. (1 mol.) of sodium thiosulfate (Na2S2O3-5H2O) in 50 cc. of water was added slowly. A vigorous reaction took place, with the evolution of heat. The reaction mixture was chilled, and the thioketone which separated was filtered off. It was washed well with water (500 cc.) and finally dried in the air. In this manner, 24.9 g. (65% yield) of thioketone were obtained. After recrystallization from methyl alcohol (410 cc. per gram of thioketone), the thioketone was obtained as scarlet needles, melting at 194 to 196 C.

Example 3.1-methyl-2-thiopropionylmethylene-p-naphthothiazoline 62.4 g. (2 mol.) of sodium sulfide were dissolved in 100 cc. of boiling water, and-the resulting solution filtered while hot. The filtered solution was cooled and added to 400 cc. of methyl alcohol.

' The resulting solution was chilled to 0 C. To

Example 4.-1-ethyl-2-thiobenzoylmethylene-c naphthothiazoline 33.1 g. (1 mol.) of l-ethyl-2-benzoylmethylene- B-naphthothiazoline were suspended in 100 cc. of dry benzene. To this suspension, 22.8 g. (1.5

mol.) of phosphorous oxychloride were added.

The resulting mixture was heated on a steam bath, so that the benzene was brought to the boiling point. The mixture was then chilled. 50 cc. of diethyl ether were added to the chilled mixture, and the chlorovinyl compound which separated was filtered off and washed with acetone.

The chlorovinyl compound thus prepared was dissolved in cc. of ethyl alcohol by heating the alcohol to boiling. To this solution was added a solution of 24.8 g. (1 mol.) of sodium thiosulfate. (NazSzO3-5Hz0) in 20 cc. of water. A vigorous reaction ensued, and the solid thioketone separated out. The reaction mixture was chilled and the thioketone filtered off. It was washed with water (200 cc.) and then stirred with 100 cc. of methyl alcohol. It was filtered from the methyl alcohol and dried in the air (yield 93%). It was twice recrystallized from methyl alcohol (900 cc. per gram of thioketone) and obtained as amber crystals, melting at 205 to 207 C. with decomposition.

Example 5.--3 ethyl-2-thioacetylmthylenebenzothiazoline 5.5 g. (1 mol.) of 2-(2-chloropropenyD-benzothiazole ethochloride were added, with stirring, to a solution of 3.2 g. (2 mol.) of sodium sulfide in a mixture of water (20 cc.) and ethyl alcohol (70 cc.). Stirring was continued for 30 minutes, during which time the thioketone separated as a solid product. The reaction mixture was allowed to stand at 0 C. for about 12 hours. The thioketone was then filtered off, washed with water (20 cc.), washed with methyl alcohol (10 cc.) and finally dried in the air. After recrystallization from methyl alcohol, the thioketone was obtained as brownish yellow crystals, melting at 142 to 144 C. with decomposition.

Example 6.5-chloro-3-ethyl-2-thiopropionylmethylenebenzothiazoline 126 g. (1 mol.) of 5-chloro-3-ethyl-2-propionylmethylene benzothiazoline were suspended in 300 cc. of dry benzene. To this suspension, chilled, were added 109 g. (1.5 mol.) of phosphorous oxychloride, with stirring. The chilled reaction product was diluted with 300 cc. of diethyl ether whereupon the chlorovinyl compound sepa rated.

The liquids were decanted from the chlorovinyl compound and it was dissolved in 500 cc. of methyl alcohol. 75 g. (2 mol.) of sodium sulfide dissolved in 100 cc. of hot water were added to the methyl alcoholic solution, with stirring. Stirring was continued for 10 minutes. The reaction mixture was then allowed to stand in the ice-box for about twelve hours. The thioketone was then filtered off, washed with water (300 cc.) and with methyl alcohol (100 cc.). It was further purified by boiling with 200 cc. of methyl alcohol solution, the thioketone was filtered oil and dried in the air (yield 33%). A portion was twice recrystallized from methyl alcohol (77 cc.

per gram of thioketone) and obtained as yellow crystals, melting at 156 to 157 C. with decomposition.

In a similar manner, 5-chloro-3-methy1-2- thiopropionylmethylenebenzoselenazoline, melting at 194 to 196 C., can be prepared.

In a manner similar to that illustrated in the above examples, 2-(2-chlorobutenyl) -benzothiazole phenochloride (see our copending application Serial No. 356,656, filed of even date herevchloropropenyl) 3,4 4 trimethylenebenzotiiiazow composition...

' ene-B-naphthothiazoline';1anda:1.9.:g.2;(1 inolrl... methyl-petoluenesulfonata:wwererheatedctogetlre onsa. .Stealllfbath: iofonezhour. nzThe: solidmeactidrrnfifi alcohol.

; I asse ses- V Efdmple with) can'be' converted into .3 phenyl f2 thidpropionylmethylenebenzotliiazolinep and? 2 lium chloride (see our copending application Se- I rial No. 356,656, filed: of evendate herewith) can be converted into"2 thioacetylmethylene-lifi-trimethylenebenzothiazoline.

From our new thioketones': valuable dye intermediates can be prepared by treatingthe thio- 'benzothi'azol'series can be"illus'trate"das follows-F The following examples illustrate the formation of dye intermediates by our new process, and

' ma formation 'ofr'dy'esiifrom" such "intermediates? Thesej examplesare'not intended to limit our id-1 venti Ei'ampll efl b (2 amethylrnercaptostyxyl) -b enzoa 1 thiazoleeetliiodidevs 3 g... (1...mol.)-.of .3-ethyl 2-?thiobenzoylniethyl enebenzothiazoline and l.9 :g. (1 mol.). .ofinethylr product was cooled and dissolved in methyl alcohol cc.) and anexcessof'pot'assium iodide in aqueous solution was added. The ethiodide which precipitated was filtered-off, washed with water cc.), with acetone- (2500.) and finally drieduirr the .-air ..(yie1d"4l.%) AfterWtwo recrys-L.

talli'z ations from methyl alcbhoimo' "cc; perigr am of.. ethiodid'el. -the .ethiodidel was obtained as..yel:-.' 4

low crystals. meltingat 2 l5 Tito .2 17 C I withldel Example 8. -2 K2;methylhiercapto l-bqitenyt) ,3

, naphthothiazole metho-p-tolunesuifonatew 7K1 l molil I of.i;l-methylrr2 thiopropionyli v I methylene-18-naphthothiazoline.-.- and $1.6 g... (1. 7

mol.) ofmethyl-p-toluenesulfonate were heated together on a steam bath for one hour. The solid 1 p-toluenesulionate..were .heated ..togethr.. on. a steam bath for one hour. The viscous reaction penyl) -benzothiazole ethiodide 2.7 g. (111101.) or 5-chloro-3-ethyl 2 thioacetylwmethylene benzothiazoline and-1.9 g. (1 mol.) of

5 methyl-p-toluenesulfonate were heated together ona steam bath for onehour; The resulting viscous mass was cooled and dissolved in 25 cc. of methyl alcohol. To this solution was added 3 g. of potassium iodide dissolved in 15 cc. ofboiling tiomz.

into dyeintermediates;

The above: dye intermediates can .be condensed;

in the presence of a basic condensing agent, such fas triethylamine, with cyclammonium quaternary salts containinga methyl group in the alpha or gamma position, such as Z-methylbenzothiazole ethiodide, 2-methylbenzothiazole pheniodide,

2-methylbenzoxazole ethiodide, 2-methylbenzo-' "selenazole :ethiodideand .lepidineaethiodide, to

give .carbocyanine z dyessrwhichsensitize .photo graphicisilverhalide .emulsions, such asgelat- In. connec-.-

inoesilversbromiodidel.-. emulsions. tionwwith.sensitization .ofphotographic .emul-. sions; it should. be. noted, however, that ..carbocy.-.

anine xdyesederived flfromcthe dye intermediate. I from 3-ethyl-2-thiofuroylmethylenebenzothiazo--- line, appear. to show no .sensitizingaction.

l. .Asthioketoneflofg the following .formula h wherein-D .represents tan-organic. radicalselectedv F from. theflsgroup consisting-.pf. phenylene and naphthylene..groups Qerepresentstan atom :selected from .the g1:oup.,consisting of sulfur and seleniumiatoms R.represents. an alkyl. group. rand H reaction productwas-cooled': and ."crushed under Rcxrepresents:anwaryl'gmupW acetone. It was filtered fromflthe acetone and dried in the air. It can beemployed without further purification.

I naphthotiiiazole' etliio'dide I 3.4. (1 men). oi:1-ethyl+2+thiobenzoylmetiiyl i product was cooled: anddissolvedsin 30 coztotsethyl To this solution werev added an excess of potassium iodide dissolved in water. The mixture was chilled and the-crystalline ethiodide which separated was filtered, washed with water (50 cc.), acetone cc.), andxfinally dried in the air. After two recrystallizations from methyl al'coholgdtawasnobtainewasa brownish yellow crys A tals;:- meltiz'rgaatulilfi to -1872" C: with rdecomposiz-w tiomh:

2. .A thioketone oftthefollowing formula-a i wherein D represents-a'phenylenesgroup, Q rep- .resents an atom selected from thgroup consisting of sulfur andselenium' atoms, R represents an alkyl group and R representsan aryl group.

3. vAthioketone ofithewfollowing. formula w'fivherein D represents a phenylene:groupflin rep- 1 h After two recrystallizations from f methyl alcbhol;'it' was obtained as brownisherys= tals, melting at 227 to 229 C. with decomposF- V Whattwe claimmas our. invention -.and..desi-re tobe-secured-by Letters .Patent of the-United States resents an alkyl group and R represents a phenyl group.

4. A thioketone of the following formula:

wherein D represents a naphthylene group, R represents an alkyl group and R represents a phenyl group.

5, 3-ethyl-2-thiobenzoylmethylenebenzothiazoline. i

6. l-ethyl-2-thiobenzoylmethylene-B-naphthothiazoline.

7. 3 ethyl-2-thiofuroy1methylenebenzothiazoline.

8. A' process for preparing a thioketone comprising treating, with a substance selected from' the group consisting of metal sulfides, ammonium sulfides, metal thiosulfates and ammonium thiosulfates, a compound of the following formula:

wherein D represents an organic radical selected from the group consisting of phenylene and naphthylene groups, Q represents an atom selected from the group consisting of sulfur and selenium atoms, R and R represent organic radi cals selected from the group consisting of alkyl and aryl groups, X represents an acid radical and X represents halogen.

9. A process for preparing a thioketone comprising treating, With a substance selected from the group consisting of metal sulfides, ammonium sulfides, metal thiosulfates and ammonium thio-- sulfates, a compound of the following formula:

wherein D represents an organic radical selected from the group consisting of phenylene and naphthylene groups, Q represents an atom selected from the group consisting of sulfur and selenium atoms, R and R represent organic radicals selected from the group consisting of alkyl and aryl groups, X represents a halide ion, and X represents halogen.

11., A process for preparing a thioketone comprising treating, with an alkali metal thiosulfate, a compound of the following formula:

wherein D represents an organic radical selected from the group consisting of phenylene and naphthylene groups, Q represents an atom selected from the group consisting of sulfur and selenium atoms, R and R represent organic radicals selected from the group consisting of alkyl and aryl groups, X represents a halide ion, and X represents halogen.

12. A process for preparing a thioketone comprising treating, with an alkali metal sulfide, a compound of the following formula:

wherein D represents a phenylene group, Q represents an atoms selected from the group consisting of sulfur and selenium atoms, R represents an alkyl group, R represents an organic radical selected from the group consisting of alkyl and aryl groups, X represents a halide ion, and X represents halogen.

13. A process for preparing a thioketone comprising treating, with an alkali metal thiosulfate, a compound of the following formula:

wherein D represents a phenylene group, Q represents an atom selected from the group consisting of sulfur and selenium atoms, R represents an alkyl group, R represents an organic radical selected from the group consisting of alkyl and aryl groups, X represents a halide ion, and X represents halogen.

14. A process for preparing a thioketone comprising treating, with an alkali metal sulfide, a compound of the following formula:

wherein D represents a naphthylene group, R represents an alkyl group, R represents an organic radical selected from the group consisting of alkyl and aryl groups, X represents a halide ion and X represents halogen.

'15. A process for preparing a thioketone comprising treating, with an alkali metal thiosulfat a compound of the following formula:

wherein D represents a naphthylene group, R represents an alkyl group, R represents an organic radical selected from the group consisting of alkyl and aryl groups, X represents a halide ion and X represents halogen.

16. A process for preparing a thioketone comprising treating, with an alkali metalsulfide, a compound of the following formula: i" D\ o- -cn=c-o1 i N/ v R 01 wherein D represents a phenylene group, R represents an alkyl group, and R. represents an organic radical selected from the group consisting of alkyl and aryl groups.

17. A process for preparing a thioketone comprising treating, with an alkali metal thiosulfate, a compound of the following formula:

wherein D represents a naphthylene group, R represents an alkyl group, and R represents an organic radical selected from the group consisting of alkyl and aryl groups.

19. A process for preparing athioketone comprising treating, with an alkali metal thiosulfate, a compound of the following formula:

wherein D represents a naphthylene group, R represents an alkyl group, and R represents an organic radical selected from the group consisting of alkyl and aryl groups.

20. Process of preparing azole compounds of the formula:

in which D is a radical completing the azole ring, .61 is an atom of the group consisting of sulphur and selenium, R is an alkyl radical, and the R1 radical is taken from the group consisting of alkyl and aryl radicals, and the group RsX is a radical of the group consisting of alkyl and aralkyl salts,

by reacting a compound of the corresponding with a compound of the group consisting of alkyl and aralkyl salts.

21. Process as defined in claim 20 in which D is a radical of the groupconsisting of phenylene and naphthalene radicals.

22. Process as defined in claim 20 and in which D is a radical of the group consisting of phenyl-' ene and naphthalene radicals and Q is sulphur.

LESLIE G. S. BROOKER. GRAFTON I-I. KEYES. 

